CN107163572A

CN107163572A - A kind of high surface energy Long Carbon Chain Polyamide transparent membrane and preparation method and purposes

Info

Publication number: CN107163572A
Application number: CN201710363179.0A
Authority: CN
Inventors: 董侠; 李璇; 王莉莉; 赵莹; 刘学新; 王笃金
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2017-05-22
Filing date: 2017-05-22
Publication date: 2017-09-15
Anticipated expiration: 2037-05-22
Also published as: CN107163572B

Abstract

The invention belongs to field of packaging material, specifically, it is related to a kind of high surface energy Long Carbon Chain Polyamide transparent membrane and preparation method and purposes.The high surface energy Long Carbon Chain Polyamide transparent membrane, it is prepared from using the raw material including Long Carbon Chain Polyamide material, the Long Carbon Chain Polyamide is polyamide of the methylene number on main chain between neighboring amide group more than or equal to 10, and the surface tension of high surface energy Long Carbon Chain Polyamide transparent membrane is 32mN/m~45mN/m.The Long Carbon Chain Polyamide material is the one or more in Long Carbon Chain Polyamide, the Long Carbon Chain Polyamide containing additive, Long Carbon Chain Polyamide alloy or Long Carbon Chain Polyamide nano composite material.The high surface energy Long Carbon Chain Polyamide transparent membrane of the present invention has that excellent mechanical property, good stability of the dimension, oil resistivity be good, barrier properties for gases is good, and show good printing performance in the case of without the surface treatment means such as corona, and there is the good transparency simultaneously, there are wide market prospects in packaging, printing technology.

Description

A kind of high surface energy Long Carbon Chain Polyamide transparent membrane and preparation method and purposes

Technical field

The invention belongs to field of packaging material, specifically, it is related to a kind of high surface energy Long Carbon Chain Polyamide transparent Film and preparation method and purposes.

Background technology

With continuing to develop for society, packing plastics film is widely used in the fields such as medicine, chemical industry and food, especially exists In terms of packaging for foodstuff, people require also more and more higher for the modification on various packaging film surfaces, for packaging film printing performance It is required that also more and more higher.Printing is carried out to plastic sheeting and is related to extremely complex physical and chemical process, by the table of plastic sheeting The influence of the factors such as surface properties, printing-ink, mode of printing, these usual factors are by the way that Plastic film surface is varied and controlled Tension force influences printing performance.

When ink is just applied to Plastic film surface, ink depends on surface tension for the infiltration of plastic sheeting Size.According to contact angle model, when surface tension and the interfacial tension sum of ink are higher than plastic sheeting critical surface tension Or difference it is little when, ink sprawls difficulty on a plastic film, and wetability is poor, the poor adhesive force of ink, air-dry after be easy to take off Fall.When the surface tension of ink is far smaller than the critical surface tension of plastic sheeting with interfacial tension sum, ink can be obtained Wetting and spreading well is obtained, the adhesive force increase between film, printing performance is greatly improved, so plastic film printing performance The key of quality is the size of film surface tension force.

Being usually used in the packaging film of printing has PP, PE, PVC etc..

PVC film is the plastic sheeting that China is just applied earliest, has rain-proof due to PVC, fire-retardant, easy-formation, close Feng Xingqiang and the low feature of cost, are widely used in packaging industry, especially do packaging label, such as " Chef Kang ", " farmer mountain The series of labels of the bottled drink such as spring ", " Wahaha ", " Coca-Cola ", but PVC film also has many deficiencies, it is maximum Shortcoming is exactly that with the addition of phthalate in PVC film, and bill 2008 editions is improved according to the Consumer Product Safety in the U.S. (CPSIA), it is proposed that phthalate must not be contained in juvenile product, it then greatly limit the application of PVC film.Application Number a kind of high transparency environment-friendly type PVC heat shrinkable printing film and its preparation are disclosed for 201010533914.6 patent application, its Phthalate is not contained in film, belongs to the PVC heat shrinkable printing films of more environmental protection, and can be extended in preparation process The production cycle of process equipment, improve PVC processing characteristics and reduce the tiny water ripples on PVC film face to increase PVC film Printing effect.But it have ignored PVC electrostatic interaction, PVC has good insulating properties, is easily caused and accumulates electricity in PVC surface Lotus, not only brings quality problems in its production and printing process, can also be produced when electrostatic is too high due to high potential guiding discharge , there is very big potential safety hazard in chemical plant in raw electric spark.

China produces various PE plastic films since 1960s, be current most widely used, consumption most A kind of big plastic film, it has excellent heat sealability, water resistance, weatherability and good chemical stability, but PE There is no polar group in molecule, polarity is poor, moistened surface tension force is low, the adhesive force with ink is very poor, even if being surface-treated, Its wetting tension declines also very fast, and this greatly reduces the printing performance of PE plastic sheetings, along with PE crystallizing power Very strong, highest crystallinity can reach 95%, can significantly reduce the transparency of PE plastic sheetings.Application No. 201210060802.2 patent application discloses BOPE coating and printing films, and it uses three layers of functional layer, sandwich layer and subfunction layer Structure is integral by biaxial tension after coextrusion, and its functional layer with the addition of the larger material of polarity, add the film Wetting tension, enhances the printing performance of BOPE coating and printing films, but it does not solve the problem of PE plastic sheetings are transparent still.

The development of China's PP plastic sheetings is started late, and PP film production line and printing system is just introduced until in October, 1980 The production line of bag.BOPP film has the advantages that excellent physical and chemical stability, mechanical strength and wearability, has become mesh Preceding most widely used printing film, but it with PE the problem of have identical, i.e. non-polar group in PP molecules, polarity are poor, its Moistened surface tension force is low, and the adhesive force with ink is very poor, causes the printing performance of PP plastic sheetings poor, along with PP belongs to knot Crystalline polymer, the transparency of PP plastic sheetings is also poor.The patent application of Application No. 201320719137.3 discloses one kind Polypropylene print film, it uses PP film layers, pretreatment layer and ink-absorbed coated layer three-decker from inside to outside, and pretreatment layer is by PP films Layer surface is obtained after carrying out electric spark processing, adds the adhesive force between PP film layers and ink-absorbed coated layer, although improve PP modelings Expect the printing performance of film, but and unresolved PP plastic sheetings it is transparent the problem of.

PA plastic sheetings are a kind of fabulous films of pliability, with very high mechanical strength, low-friction coefficient, good On chemical proofing and excellent heat resistance, strand have amide group, therefore, intramolecular and it is intermolecular can be with shape Into hydrogen bond, PA plastic sheetings have polarity, are favorably improved its printing performance.But the amide group density of common polyamide is very Greatly, with very big water imbibition, dimensional stability is poor, shrinkage factor increase.

Long Carbon Chain Polyamide is compared with common polyamide, containing longer methene chain, both with stronger hydrogen bond action, Again because the reduction of amide group density causes the increase of molecule chain flexibility, the water imbibition of material, therefore long carbon are greatly reduced Chain polyamide is in addition to possessing the characteristics of common polyamide is strong and tough, the also dimensional stability with better than common polyamide, gas Body barrier and oil resistivity, can for a long time be used, the temperature being used for a long time in inert gas is 110 DEG C and made in 100 DEG C of oil With safety, in addition also there is good moulding processability, general Maranyl film is overcome in application field Limitation, meets its performance requirement in the application, up to the present, there is not yet preparing high surface with Long Carbon Chain Polyamide The Patents and report of the transparent printing film of energy.

In view of this it is special to propose the present invention.

The content of the invention

The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art poly- there is provided a kind of high surface energy Long carbon chain Acid amides transparent membrane.Described high surface energy Long Carbon Chain Polyamide transparent membrane has excellent mechanical property, dimensional stability Well, and in the case of without the surface treatment means such as corona good printing performance is shown, and is had simultaneously good The good transparency, has wide market prospects in packaging, printing technology.

In order to solve the above technical problems, the present invention is using the basic conception of technical scheme：

A kind of high surface energy Long Carbon Chain Polyamide transparent membrane, using the raw material preparation including Long Carbon Chain Polyamide material Into the Long Carbon Chain Polyamide is polyamide of the methylene number on main chain between neighboring amide group more than or equal to 10, high The surface tension of surface energy Long Carbon Chain Polyamide transparent membrane is 32mN/m~45mN/m.

Can by adjusting the technological parameters such as the hauling speed during the barrel zone temperature in extruder, mold temperature and blown film The controllability of the properties such as transparency and surface tension to realize high surface energy Long Carbon Chain Polyamide transparent membrane.

And the Combination of Long Carbon Chain Polyamide material and other components is good, can be with other macromolecules, auxiliary agent, increasing Just, toughening auxiliary agent etc. is combined, and prepares the composite membrane of different function requirements.

Long Carbon Chain Polyamide has stronger intramolecular and intermolecular hydrogen bond action, before this invention is filed, ability Field technique personnel think its poor processability when preparing film according in general theory, it is difficult to obtain good properties Film, and before because its cost also relative other polymers is high, technical staff thinks to be unworthy research.

And present inventor has found described Long Carbon Chain Polyamide during stretching and alternating temperature in experimentation With a sensitive phase transition temperature region, i.e. Brill transition temperatures are within the scope of 80-130 DEG C, and it can be easy to Ground regulates and controls to occur under normal process condition.Brill transformations refer to the turning from alpha-crystal form to γ crystal formations in certain temperature range Become, and external force field has regulating and controlling effect to Brill.Long Carbon Chain Polyamide is under the specified conditions during film produces and processes engineering by α Crystalline substance is changed into γ crystalline substances, and the transformation to assign the film preferably property prepared, and toughness increase, loose performance are improved, significantly carried High processing characteristics, while improving the printing transfer amount of ink.Due to being unaware that Long carbon chain before those of ordinary skill The influence that the Brill transformations of polyamide are brought to thin-film material performance, it is thus regarded that it is unsuitable for preparing film.Present techniques The experimental result of scheme is different with the conclusion obtained by the cognitive supposition before those of ordinary skill, has opened up field of film preparation New approaches, and the film has wide market-oriented prospect.

High surface energy Long Carbon Chain Polyamide transparent membrane of the present invention is tested through printing, without any surface treatment In the case of (such as sided corona treatment), directly passed through the soft version of ink and letterpress, typographic pattern or word are clearly and not It is easy to fall off, it is not necessary to numerous and diverse aid in treatment, process, time and energy consumption are saved, with good printing prospect, with great Convenience.Preferably, the Long Carbon Chain Polyamide material is Long Carbon Chain Polyamide, the Long Carbon Chain Polyamide containing additive, long carbon One or more in chain polyamide alloy or Long Carbon Chain Polyamide nano composite material.

Wherein, described additive include nucleator, antioxidant, chain extender, Long Carbon Chain Polyamide alloy material include PP, The reinforcing material such as PA Polymer materials and glass fibre, whisker, nano composite material includes CNT, montmorillonite, charcoal It is black etc..

The consumption of additive is the 0.2%~1.5% of Long Carbon Chain Polyamide quality of materials.The consumption of the additive can be true Protecting film has more preferable transparency and obdurability, and can also improve the printing performance of film.

Preferably, the high surface energy Long Carbon Chain Polyamide transparent membrane has single layer structure or sandwich construction；

The sandwich construction includes top layer and intermediate layer, and the top layer uses Long Carbon Chain Polyamide material, the intermediate layer Using the one or more in polyolefin and polyamide material.

Preferably, the fusing point of Long Carbon Chain Polyamide material is 180 DEG C~220 DEG C, and melt index is 1~2 0g/10min.

Here, described melt index test condition is：Counterbalance mass 2.16kg, 235 DEG C of test temperature.

Preferably, in the preparation process of the high surface energy Long Carbon Chain Polyamide transparent membrane, Long Carbon Chain Polyamide material Occurs the transformation from alpha-crystal form to γ crystal formations.

Obvious crystal transfer phenomenon is there occurs in the drawing process of high surface energy Long Carbon Chain Polyamide transparent membrane, by α crystalline substances are changed into γ crystalline substances, what this crystal transfer Brill had found in PA66 temperature-rise periods first in nineteen forty-two, so being referred to as Brill changes, and brilliant a large amount of γ formation is dual from crystal transfer (alpha-crystal form is changed into γ crystal formations) and stretching induction crystallization Contribution.

Preferably, the thickness of the high surface energy Long Carbon Chain Polyamide transparent membrane is 10 μm -100 μm, it is highly preferred that institute The thickness for stating high surface energy Long Carbon Chain Polyamide transparent membrane is 40 μm -80 μm；

Preferably, the surface tension of high surface energy Long Carbon Chain Polyamide transparent membrane is 36mN/m~45mN/m；

Preferably, the light transmittance of high surface energy Long Carbon Chain Polyamide transparent membrane is 90%~100%.

The high surface energy Long Carbon Chain Polyamide transparent membrane is in the feelings without any surface treatment (such as sided corona treatment) Because itself has higher surface tension under condition, can directly carry out printing and use, at present by the soft version of UV ink and Letterpress, carries out printing and uses after can also being surface-treated.

Preferably, the Long Carbon Chain Polyamide is NYLON610, nylon 612, nylon 1010, Nylon 1012 or nylon 1212 In one or more, more preferably nylon 1010 (nylon 1010), Nylon 1012 and nylon 1212.

There is amide group on the strand of above-described Long Carbon Chain Polyamide, there is good pole compared with polyolefin Property, at the same the density of amide group again be less than common nylon 6 and nylon66 fiber, with more preferable hydrophobicity, gathered polyamide and Both sides' advantage of polyolefin, performance is more excellent.

Another free-revving engine of the present invention is to provide any one high surface energy Long carbon chain polyamides described in more than one The preparation method of amine transparent membrane, methods described be blowing, rolling process or the tape casting, wherein, the blowing include it is following Step：

(1) pellet is dried in vacuum drying oven, the pellet includes Long Carbon Chain Polyamide material；

(2) blown film is carried out；

(3) film that step (2) is produced by boasting is drawn and wound, through cooling and shaping, produced.

Preferably, in step (2), pellet first by twin-screw plastify extrude, then by mouth mold carry out tubular film base into Type, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the temperature control in the area of mould two are 200 DEG C -300 DEG C, screw speed For 10rpm~100rpm, obtained tubular film base is subjected to inflation by compressed air under melt flows state, blown film is controlled Vesicle diameter is 50~2000mm；

By above-mentioned temperature control, screw speed regulation and the mutual cooperation of blown film vesicle diameter, Long carbon chain is promoted to gather Thorough transformation from from alpha-crystal form to γ crystal formations occurs during stretching and alternating temperature for acid amides, and crystal thickness is evenly distributed suitably, order system The film obtained has appropriate polarity with while obtaining high surface tension and excellent printing performance.

It is highly preferred that in step (3), the hauling speed of hauling machine is 1rpm~100rpm, and the rolling speed of winder is 1rpm~100rpm.

Using described hauling speed and rolling speed, and the regulation of foregoing temperature control, screw speed and blown film Vesicle diameter comprehensive regulation so that the transparency of film is higher, and the malleable of film gets a promotion.

Preferably, described rolling process comprises the following steps：

Pellet is plastified by twin-screw and extruded, then carries out laminar film base shaping, the area of machine barrel one of extruder, machine by mouth mold 2nd area of cylinder, the area of mould one, the area's temperature control of mould two are 200 DEG C~300 DEG C, and screw speed is 10rpm~100rpm, will be obtained Laminar film base under melt flows state by two roll calender extrusion calendaring film forming, the temperature of stack is 200 DEG C~300 DEG C, then directly fitted with cloth base under stack film is made；

By the temperature of above-mentioned temperature control, screw speed regulation and stack, promote Long Carbon Chain Polyamide in stretching With occur the thorough transformation from alpha-crystal form to γ crystal formations during alternating temperature, obtained film has appropriate polarity to obtain simultaneously High surface tension and excellent printing performance.

Preferably, described the tape casting comprises the following steps：

Pellet is plastified by twin-screw and extruded, then carries out laminar film base shaping by T-type structure mould, extruder The area of machine barrel one, the area of machine barrel two, the area of mould one, the area of mould two temperature be 200 DEG C~300 DEG C, screw speed be 10rpm~ 100rpm, obtained laminar film base is cast in the form of sheets under melt flows state the roll surface of the cooling roller rotated smoothly On, diaphragm is through the sizing that cools on cooling roller, and there is the nozzle length air knife consistent with roll surface width cooling roller side, spray Mouthful gap is 0.5mm~2mm, and air knife blast is 98kPa~-980kPa, the hauling speed for control hauling machine be 1rpm~ 100rpm, the rolling speed of winder wind for 1rpm~100rpm, by product.

By above-mentioned temperature control, screw speed regulation, spout gap, air knife blast, hauling speed and rolling speed, Promote Long Carbon Chain Polyamide that the thorough transformation from alpha-crystal form to γ crystal formations, obtained film tool occur during stretching and alternating temperature There is appropriate polarity to obtain high surface tension and excellent printing performance simultaneously, and film has more preferable transparency, more Plus it is bright and clean have no time, texture is more preferable.

The another free-revving engine of the present invention is to provide a kind of by the above-mentioned high surface energy Long Carbon Chain Polyamide of any one Transparent membrane directly applies to packaging material, the purposes of printing technology.

After adopting the above technical scheme, the present invention has the advantages that compared with prior art：

(1) contain polar amide groups on Long Carbon Chain Polyamide strand, intramolecular and it is intermolecular can form hydrogen bond, So that Long Carbon Chain Polyamide plastic sheeting has certain polarity, with high surface tension, its printing performance is significantly improved, In the case of without any surface treatment (such as sided corona treatment), its surface tension is also much larger than PP and PE plastic sheetings；

(2) Long Carbon Chain Polyamide, containing longer methene chain, was both made compared with common polyamide with stronger hydrogen bond With, and because the reduction of amide group density causes the increase of molecule chain flexibility, the water imbibition of material is greatly reduced, therefore, Long Carbon Chain Polyamide is in addition to possessing the characteristics of common polyamide is strong and tough, the also dimensional stability with better than common polyamide And moulding processability, overcome limitation of the general Maranyl film in application field, meet it in the application Performance requirement；

(3) interaction of the hydrogen bond of Long Carbon Chain Polyamide causes it to belong to semicrystalline polymeric, and transparency should It is relatively low, but in film forming procedure, due to there occurs the change of crystal formation, and crystal thickness distribution is changed, and improves film Transparency；

Can by adjusting the technological parameters such as the hauling speed during the barrel zone temperature in extruder, mold temperature and blown film To realize the controllability of film thickness, transparency and surface tension etc.；

(4) membrane preparation method is melting extrusion upper blowing method, lower blowing method, puts down and blow method and the tape casting, it is not necessary to solvent, is prepared Technique is simple and environmentally-friendly, along with itself does not need substantial amounts of additive component, more environmentally-friendly, science.

Brief description of the drawings

Accompanying drawing is as the part of the present invention, and for providing further understanding of the invention, of the invention is schematic Embodiment and its illustrate to be used to explain the present invention, but do not constitute inappropriate limitation of the present invention.Obviously, drawings in the following description Only some embodiments, to those skilled in the art, on the premise of not paying creative work, can be with Other accompanying drawings are obtained according to these accompanying drawings.In the accompanying drawings：

Fig. 1 a are the SEM figures of the high surface energy Long Carbon Chain Polyamide transparent membrane of the embodiment of the present invention 1；

Fig. 1 b are the SEM figures of the high surface energy Long Carbon Chain Polyamide transparent membrane of the embodiment of the present invention 1；

Fig. 2 be the raw particles and high surface energy Long Carbon Chain Polyamide transparent membrane of the embodiment of the present invention 1 at room temperature 1D WAXS curve maps；

Fig. 3 is the DCS curve maps of the high surface energy Long Carbon Chain Polyamide transparent membrane of the embodiment of the present invention 1；

Fig. 4 is the experiment knot for the high surface energy Long Carbon Chain Polyamide transparent membrane wetting tension for determining the embodiment of the present invention 1 Fruit is schemed.

It should be noted that these accompanying drawings and word description are not intended as the design model for limiting the present invention in any way Enclose, but be that those skilled in the art illustrate idea of the invention by reference to specific embodiment.

Embodiment

To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention In accompanying drawing, the technical scheme in embodiment is clearly and completely described, following examples be used for illustrate the present invention, but It is not limited to the scope of the present invention.

Embodiment 1

(1) raw material PA612 will be included and the pellet of chain extender (0.5%) is dried in vacuum drying oven；

(2) pellet is plastified by twin-screw extrude first, and PA612 fusing points are 220 DEG C, melt index 20g/10min, then are led to Cross mouth mold and carry out tubular film base shaping, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 220 DEG C, 240 DEG C, 260 DEG C, 300 DEG C, screw speed is 10rpm, by obtained tubular film base under melt flows state pass through compression Air carries out inflation, and blown film vesicle diameter is 200mm；

(3) film that step (2) is produced by boasting is drawn and wound, hauling machine hauling speed is 10rpm, winder winding Speed is 10rpm, through cooling and shaping, is produced.

The high surface energy Long Carbon Chain Polyamide transparent membrane prepared, film thickness is 50 μm, measures its surface tension For 36mN/m, light transmittance is 98%.

Embodiment 2

(1) pellet of PA1212/PP alloys is dried in vacuum drying oven；

(2) pellet is plastified by twin-screw extrude first, and PA1212 fusing points are 180 DEG C, and PP fusing points are 163 DEG C, and melting refers to Number 20g/10min, then tubular film base shaping, the area of extruder barrel one, the area of machine barrel two, the area of mould one, mould are carried out by mouth mold Two area's temperature are respectively 200 DEG C, 220 DEG C, 240 DEG C, 240 DEG C, and screw speed is 20rpm, by obtained tubular film base in melt Inflation is carried out by compressed air under flow regime, blown film vesicle diameter is 50mm；

(3) film that step (2) is produced by boasting is drawn and wound, hauling machine hauling speed is 20rpm, winder winding Speed is 20rpm, through cooling and shaping, is produced.

The high surface energy Long Carbon Chain Polyamide transparent membrane prepared, film thickness is 100 μm, measures its surface tension For 40mN/m, light transmittance is 85%.

Embodiment 3

(1) pellet of PA1010/ glass fiber alloys is dried in vacuum drying oven；

(2) pellet is plastified by twin-screw extrude first, and PA1010 fusing points are 190 DEG C, and glass fibre fusing point is 680 DEG C, Melt index 15g/10min, then tubular film base shaping, the area of extruder barrel one, the area of machine barrel two, mould one are carried out by mouth mold Area, the area's temperature of mould two are respectively 220 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, and screw speed is 100rpm, by obtained tubular film Base carries out inflation under melt flows state by compressed air, and blown film vesicle diameter is 2000mm；

(3) film that step (2) is produced by boasting is drawn and wound, hauling machine hauling speed is 100rpm, winder is received Volume speed is 100rpm, through cooling and shaping, is produced.

The high surface energy Long Carbon Chain Polyamide transparent membrane prepared, film thickness is 10 μm, measures its surface tension For 45mN/m, light transmittance is 90%.

Embodiment 4

(1) pellet of PA1010/ whisker alloys is dried in vacuum drying oven；

(2) pellet is plastified by twin-screw extrude first, and PA1010 fusing points are 190 DEG C, melt index 15g/10min, then Tubular film base shaping is carried out by mouth mold, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 220 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, screw speed is 100rpm, and obtained tubular film base is passed through under melt flows state Compressed air carries out inflation, and blown film vesicle diameter is 2000mm；

The high surface energy Long Carbon Chain Polyamide transparent membrane prepared, film thickness is 10 μm, measures its surface tension For 38mN/m, light transmittance is 70%.

Embodiment 5

(1) PA1010 pellet is dried in vacuum drying oven；

(2) pellet is plastified by twin-screw extrude first, and PA1010 fusing points are 190 DEG C, melt index 15g/10min, then Tubular film base shaping is carried out by mouth mold, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 240 DEG C, 260 DEG C, 280 DEG C, 300 DEG C, screw speed is 30rpm, and obtained tubular film base is passed through under melt flows state Compressed air carries out inflation, and blown film vesicle diameter is 200mm；

(3) film that step (2) is produced by boasting is drawn and wound, hauling machine hauling speed is 30rpm, winder winding Speed is 30rpm, through cooling and shaping, is produced.

The high surface energy Long Carbon Chain Polyamide transparent membrane prepared, film thickness is 50 μm, measures its surface tension For 34mN/m, light transmittance is 100%.

Embodiment 6

(1) PA1012 pellet is dried in vacuum drying oven；

(2) pellet is plastified by twin-screw extrude first, and PA1012 fusing points are 185 DEG C, melt index 20g/10min, then Tubular film base shaping is carried out by mouth mold, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 220 DEG C, 240 DEG C, 260 DEG C, 300 DEG C, screw speed is 100rpm, and obtained tubular film base is passed through under melt flows state Compressed air carries out inflation, and blown film vesicle diameter is 80mm；

The high surface energy Long Carbon Chain Polyamide transparent membrane prepared, film thickness is 80 μm, measures its surface tension For 42mN/m, light transmittance is 99%.

Embodiment 7

(1) PA612 pellet is dried in vacuum drying oven；

(2) pellet is plastified by twin-screw extrude first, and PA612 fusing points are 220 DEG C, melt index 15g/10min, then are led to Cross mouth mold and carry out tubular film base shaping, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 240 DEG C, 260 DEG C, 280 DEG C, 300 DEG C, screw speed is 60rpm, by obtained tubular film base under melt flows state pass through compression Air carries out inflation, and blown film vesicle diameter is 100mm；

(3) film that step (2) is produced by boasting is drawn and wound, hauling machine hauling speed is 50rpm, winder winding Speed is 50rpm, through cooling and shaping, is produced.

The high surface energy Long Carbon Chain Polyamide transparent membrane prepared, film thickness is 70 μm, measures its surface tension For 38mN/m, light transmittance is 95%.

Embodiment 8

(1) PA610 pellet is dried in vacuum drying oven；

(2) pellet is plastified by twin-screw extrude first, and PA610 fusing points are 220 DEG C, melt index 15g/10min, then are led to Cross mouth mold and carry out tubular film base shaping, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 240 DEG C, 260 DEG C, 280 DEG C, 280 DEG C, screw speed is 20rpm, by obtained tubular film base under melt flows state pass through compression Air carries out inflation, and blown film vesicle diameter is 400mm；

The high surface energy Long Carbon Chain Polyamide transparent membrane prepared, film thickness is 40 μm, measures its surface tension For 36mN/m, light transmittance is 97%.

It is embodiment 9-20 below, operating procedure is shown in Table 1 and table referring to embodiment 1, specific process parameter and performance indications 2。

The embodiment 9-14 of table 1 technological parameter and film performance parameter

The embodiment 15-20 of table 2 technological parameter and film performance parameter

Example 2 below 1-29 prepares film using rolling process.

Embodiment 21

Melting extrusion is carried out to raw material PA1012 and prepares melt, PA1012 fusing points are 185 DEG C, melt index 10g/ 10min, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 240 DEG C, 260 DEG C, 280 DEG C, 280 DEG C, screw speed is 20rpm；

Pressing mold is carried out by rolling process to the melt of extruded machine melting extrusion again, calendering roll temperature is 200 DEG C, then with cloth Film is made in laminating to base directly under stack.

Obtained film thickness is 60 μm, measures its surface tension for 38mN/m, and the light transmittance for measuring film is 99%.

Embodiment 22

Melting extrusion is carried out to raw material PA612 and prepares melt, PA612 fusing points are 220 DEG C, melt index 17g/ 10min, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 250 DEG C, 280 DEG C, 280 DEG C, 300 DEG C, screw speed is 10rpm；

Pressing mold is carried out by rolling process to the melt of extruded machine melting extrusion again, calendering roll temperature is 300 DEG C, then with cloth Film is made in laminating to base directly under stack.

Obtained film thickness is 50 μm, measures its surface tension for 36mN/m, and the light transmittance for measuring film is 95%.

Embodiment 23

Melting extrusion is carried out to raw material PA610 and prepares melt, PA610 fusing points are 220 DEG C, melt index 17g/ 10min, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 250 DEG C, 280 DEG C, 290 DEG C, 290 DEG C, screw speed is 20rpm；

Pressing mold is carried out by rolling process to the melt of extruded machine melting extrusion again, calendering roll temperature is 280 DEG C, then with cloth Film is made in laminating to base directly under stack.

Obtained film thickness is 65 μm, measures its surface tension for 36mN/m, and the light transmittance for measuring film is 95%.

It is below embodiment 24-29, operating procedure such as embodiment 21, specific process parameter and film performance index are shown in Table 3.

The embodiment 24-29 of table 3 technological parameter and film performance index

Example 3 below 0-37 prepares film using the tape casting.

Embodiment 30

Melting extrusion is carried out to raw material PA1012 and prepares melt, PA1012 fusing points are 185 DEG C, melt index 15g/ 10min, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 240 DEG C, 260 DEG C, 280 DEG C, 280 DEG C, screw speed is 20rpm；

The melt of extruded machine melting extrusion is filmed by the tape casting again, spout gap is 0.5mm, air knife blast For 98kPa, hauling machine hauling speed is 20rpm, and winder rolling speed is 20rpm.

Obtained film thickness is 50 μm, measures its surface tension for 36mN/m, and the light transmittance for measuring film is 90%.

Embodiment 31

Melting extrusion is carried out to raw material PA612 and prepares melt, PA612 fusing points are 220 DEG C, melt index 10g/ 10min, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the area's temperature of mould two are respectively 240 DEG C, 260 DEG C, 280 DEG C, 280 DEG C, screw speed is 10rpm；

The melt of extruded machine melting extrusion is filmed by the tape casting again, spout gap is 2mm, air knife blast is 980kPa, hauling machine hauling speed is 20rpm, and winder rolling speed is 20rpm.

Obtained film thickness is 70 μm, measures its surface tension for 38mN/m, and the light transmittance for measuring film is 99%.

Following embodiment 32-37, operating procedure is with reference to embodiment 30, and specific process parameter and film performance index are shown in Table 4。

The embodiment 32-37 of table 4 technological parameter and film performance parameter

Test example 1

This test example has investigated the mechanical property of high surface energy Long Carbon Chain Polyamide transparent membrane of the present invention.

High surface energy Long Carbon Chain Polyamide transparent membrane that embodiment 1 obtains is characterized along differently- oriented directivity and perpendicular to taking To direction tensile property, the concrete numerical value of tensile strength, elongation at break and toughness (stress-strain diagram area under) referring to Table 5.

From experimental result as can be seen that film prepared by the embodiment of the present invention has preferable tensile property, along orientation The film in direction perpendicular to the film of differently- oriented directivity than showing preferable tensile strength and toughness.

The mechanical property of the film of table 5

Test example 2

The pattern of the high surface energy Long Carbon Chain Polyamide transparent membrane of the embodiment of the present invention 1 has been investigated in this experiment using SEM Situation, its specific pattern is referring to Fig. 1 a and Fig. 1 b.

SEM figures from gained are it can be seen that the high surface energy Long Carbon Chain Polyamide thin transparent that the embodiment of the present invention is prepared Film surface smooth even.

Test example 3

The high surface energy Long Carbon Chain Polyamide that this experiment characterizes the raw particles of embodiment 1 and finally prepared is transparent The 1D WAXS curves of film at room temperature, are shown in Fig. 2.

And the high surface energy Long Carbon Chain Polyamide thin transparent for characterizing the raw particles of embodiment 1 and finally preparing The hot property contrast of film, is shown in Fig. 3.

From figure 2 it can be seen that typical alpha-crystal form is presented in resin at room temperature, γ crystal formations are presented in film at room temperature.From Fig. 3 can be seen that raw pellets and occur at 184.18 DEG C unimodal, and high surface energy Long Carbon Chain Polyamide transparent membrane is 181.45 DEG C and 189.44 DEG C at occur it is bimodal, crystal thickness distribution broadens so that high surface energy Long Carbon Chain Polyamide transparent membrane have There are high tenacity and tensile strength and high transparency.

Test example 4

This experiment characterizes the wetting tension of the high surface energy Long Carbon Chain Polyamide transparent membrane of embodiment 1 at room temperature, Tests concrete steps and result are as follows.

For determining matching somebody with somebody when for the mixed solution used in the wetting tension of high surface energy Long Carbon Chain Polyamide transparent membrane The corresponding wetting tension of high surface energy Long Carbon Chain Polyamide transparent membrane, as shown in table 6.

The mixed solution of table 6 is with when wetting tension

Wetting tension/(mN/m)	Ethylene glycol ethyl ether/mL	Formamide/mL
			40	1.825	3.175
38	2.3	2.7
			37	2.575	2.425
36	2.875	2.125
			34	3.675	1.325
30	5	0

Six groups of mixed solutions are respectively configured according to the proportioning in table 6, a little victoria blue B are separately added into as dyeing Agent, is well mixed it, promptly smears one layer in film inner surface with swab stick respectively and (smears traction of the direction perpendicular to blown film Direction), the time (being defined to be shunk along draw direction) that the fluid film of its formation is started to shrink at from continuous state is observed, if Time is less than 2S, then is repeated to test on a new sample with the mixed solution with smaller wetting tension, connect until finding 2S mixed solution is bordering on, parallel testing is matched until at least three times all close to 2S with this, then with the wetting of the mixed solution Tension force is as the wetting tension of sample, and it is the experimental result picture for determining film wetting tension as a result to see Fig. 4, Fig. 4, is finally measured Wetting tension is 36mN/m.

Fig. 4 middle and upper parts bottle is the mixed solution of different ratio, adds victoria blue B as coloring agent, display is blue The profit of mark numeral correspondence mixed solution after the sequence number of mark numeral correspondence mixed solution before color, its strigula, strigula Wet tension value, unit is mN/m, and the order of sequence number from small to large corresponds to the order of the wetting tension of mixed solution from big to small；Under Portion is the result after 10min after film inner surface smearing, and it is corresponding with the sequence number difference of top bottle that it marks numeral.

Described above is only presently preferred embodiments of the present invention, not makees any formal limitation to the present invention, though So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any technology people for being familiar with this patent Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompting make it is a little change or be modified to The equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit pair according to the present invention Any simple modification, equivalent variations and modification that above example is made, in the range of still falling within the present invention program.

Claims

1. a kind of high surface energy Long Carbon Chain Polyamide transparent membrane, it is characterised in that using includes Long Carbon Chain Polyamide material Raw material is prepared from, and the Long Carbon Chain Polyamide is that the methylene number on main chain between neighboring amide group is more than or equal to 10 Polyamide, the surface tension of the Long Carbon Chain Polyamide transparent membrane of high surface energy is 32mN/m~45mN/m.

2. high surface energy Long Carbon Chain Polyamide transparent membrane according to claim 1, it is characterised in that the Long carbon chain gathers Amide material is Long Carbon Chain Polyamide, the Long Carbon Chain Polyamide containing additive, Long Carbon Chain Polyamide alloy or Long Carbon Chain Polyamide One or more in nano composite material.

3. high surface energy Long Carbon Chain Polyamide transparent membrane according to claim 1 or 2, it is characterised in that the high table The Long Carbon Chain Polyamide transparent membrane of face energy has single layer structure or sandwich construction；

The sandwich construction includes top layer and intermediate layer, and the top layer uses Long Carbon Chain Polyamide material, and the intermediate layer is used One or more in polyolefin and polyamide material.

4. the high surface energy Long Carbon Chain Polyamide transparent membrane according to claim any one of 1-3, it is characterised in that long carbon The fusing point of chain polyamide material is 180 DEG C~220 DEG C, and melt index is 1~2 0g/10min.

5. the high surface energy Long Carbon Chain Polyamide transparent membrane according to claim any one of 1-4, it is characterised in that described In the preparation process of the Long Carbon Chain Polyamide transparent membrane of high surface energy, Long Carbon Chain Polyamide material occurs brilliant from alpha-crystal form to γ The transformation of type.

6. the high surface energy Long Carbon Chain Polyamide transparent membrane according to claim any one of 1-5, it is characterised in that described The thickness of the Long Carbon Chain Polyamide transparent membrane of high surface energy is 10 μm -100 μm, it is preferable that the Long carbon chain of the high surface energy The thickness of polyamide transparent membrane is 40 μm -80 μm；

7. the high surface energy Long Carbon Chain Polyamide transparent membrane according to claim any one of 1-6, it is characterised in that described The surface tension of the Long Carbon Chain Polyamide transparent membrane of high surface energy is 32mN/m~45mN/m, it is preferable that the high surface energy Long Carbon Chain Polyamide transparent membrane surface tension be 36mN/m~45mN/m.

8. a kind of preparation method of the high surface energy Long Carbon Chain Polyamide transparent membrane described in any one of claim 1-7, it is special Levy and be, methods described be blowing, rolling process or the tape casting, wherein, the blowing comprises the following steps：

(2) blown film is carried out；

9. preparation method according to claim 8, it is characterised in that in step (2), pellet is plastified by twin-screw first Extrusion, then tubular film base shaping, the area of extruder barrel one, the area of machine barrel two, the area of mould one, the temperature in the area of mould two are carried out by mouth mold Degree control is 200 DEG C -300 DEG C, and screw speed is 10rpm~100rpm, by obtained tubular film base under melt flows state Inflation is carried out by compressed air, it is 50~2000mm to control blown film vesicle diameter；

Preferably, in step (3), the hauling speed of hauling machine is 1rpm~100rpm, the rolling speed of winder for 1rpm~ 100rpm；

Preferably：

Described rolling process comprises the following steps：

Pellet is plastified by twin-screw and extruded, then carries out laminar film base shaping, the area of machine barrel one of extruder, machine barrel two by mouth mold Area, the area of mould one, the area's temperature control of mould two are 200 DEG C~300 DEG C, and screw speed is 10rpm~100rpm, by obtained piece Shape film base is by two roll calender extrusion calendaring film forming under melt flows state, and the temperature of stack is 200 DEG C~300 DEG C, Directly fitted again with cloth base under stack and film is made；

Described the tape casting comprises the following steps：

Pellet is plastified by twin-screw and extruded, then carries out laminar film base shaping, the machine barrel of extruder by T-type structure mould One area, the area of machine barrel two, the area of mould one, the temperature in the area of mould two are 200 DEG C~300 DEG C, and screw speed is 10rpm~100rpm, Obtained laminar film base is cast on the roll surface of the cooling roller rotated smoothly in the form of sheets under melt flows state, diaphragm exists Through the sizing that cools on cooling roller, there is the nozzle length air knife consistent with roll surface width cooling roller side, and spout gap is 0.5mm~2mm, air knife blast is 98kPa~-980kPa, and the hauling speed for controlling hauling machine is 1rpm~100rpm, winder Rolling speed be 1rpm~100rpm, wind product.

10. a kind of high surface energy Long Carbon Chain Polyamide transparent membrane by described in claim 1-7 any one is applied to packaging The purposes of material, printing technology.